EP0047206B1 - Process for preparation of aminoalcohols polyoxa-alkylated or polyoxa-arylated and their use as cation complexing agents - Google Patents

Process for preparation of aminoalcohols polyoxa-alkylated or polyoxa-arylated and their use as cation complexing agents Download PDF

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Publication number
EP0047206B1
EP0047206B1 EP81401325A EP81401325A EP0047206B1 EP 0047206 B1 EP0047206 B1 EP 0047206B1 EP 81401325 A EP81401325 A EP 81401325A EP 81401325 A EP81401325 A EP 81401325A EP 0047206 B1 EP0047206 B1 EP 0047206B1
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amine
bis
equal
aza
formula
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EP0047206A1 (en
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Louis Linguenheld
Gérard Soula
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Rhone Poulenc Specialites Chimiques
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C213/00—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton
    • C07C213/02—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton by reactions involving the formation of amino groups from compounds containing hydroxy groups or etherified or esterified hydroxy groups

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  • the present invention relates to a process for the preparation of polyoxaalkylated or polyoxaarylated amino alcohols which can be used as cation complexing agents.
  • Polyoxaalkylated amino alcohols have already been described. These include (English Patent No. 897,163) those having the formula:
  • nickel catalysts of the Raney or Harshaw nickel type; the amount of catalyst may be between 1 and 15% of the weight of bis (polyoxaalkyl) amine or bis (polyoxaaryl) amine and preferably between 2 and 6%.
  • the polyalkylene glycol molar ratio of formula (II) / bis (polyoxaalkyl) amine or bis (polyoxaaryl) amine of formula (III) may also be between 1, 5 and 10 times the stoichiometry and preferably between 2 and 6 times the stoichiometry .
  • the process which is the subject of the invention may preferably be carried out in the presence of hydrogen, at a pressure below 20 bars, and generally at autogenous pressure, with vigorous stirring until the polyalkylene glycol disappears; this operation lasts from 2 to 10 hours and general 3 to 4 hours.
  • the amount of hydrogen that can be used is of the order of 1 to 10% of the weight of alkylene glycol used and preferably of the order of 1 to 5%.
  • the water formed during the reaction can be removed from the reaction medium using a gas stream, such as hydrogen when the latter has been used or nitrogen.
  • the polyoxaalkylated or polyoxaarylated amino alcohols obtained according to the process of the invention can be used as cation complexing agents.
  • the present invention also relates to this application.
  • the yield reaches 55% on the secondary amine used.
  • the yield on the charged secondary amine reaches 71%.
  • the yield relative to the secondary amine used is 71.5%.
  • the yield relative to the secondary amine is 72%.
  • the test is also carried out in the absence of complexing agent to be tested.
  • Example 6 The test described in Example 6 is carried out using as a complexing agent to test the product of Example 4.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
  • Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)

Abstract

Novel polyoxaalkyl aminoalcohols, well adapted for the complexation/solubilization of a wide variety of cations, have the structural formula: <IMAGE>

Description

La présente invention vise un procédé de préparation d'aminoalcools polyoxaalkylés ou polyoxaarylés pouvant être utilisés comme agents de complexation de cations.The present invention relates to a process for the preparation of polyoxaalkylated or polyoxaarylated amino alcohols which can be used as cation complexing agents.

Des aminoalcools polyoxaalkylés ont déjà été décrits. Il s'agit notamment (brevet anglais no 897 163) de ceux ayant pour formule:

Figure imgb0001
Polyoxaalkylated amino alcohols have already been described. These include (English Patent No. 897,163) those having the formula:
Figure imgb0001

Ils peuvent être préparés par action d'une alca- nolamine HO-alkylène-NH2 sur par exemple un chlorure d'alkoxypolyéthylèneoxyéthyl:

Figure imgb0002
They can be prepared by the action of an alkolamine HO-alkylene-NH 2 on, for example, an alkoxypolyethyleneoxyethyl chloride:
Figure imgb0002

Il est connu d'après le brevet français no 2402473 de préparer des di(hydroxypolyoxaal- kyl)mono(alkylétherpolyoxaaryl)amine par oxy- éthylation d'une amine à fonction éther obtenue par propoxylation d'un alcool suivie d'une ammo- nolyse.It is known from French patent no. 2402473 to prepare di (hydroxypolyoxaalkyl) mono (alkyl etherpolyoxaaryl) amine by oxyethylation of an amine with an ether function obtained by propoxylation of an alcohol followed by ammonolysis .

Il a également été proposé dans le brevet européen no 5094 de préparer des tris(polyoxaal- kyl)amines par action d'un sel de métal alcalin d'un monoalcoyléther d'une éthylène glycol et d'une tris(halogénoéthyl)amine.It has also been proposed in European Patent No. 5094 to prepare tris (polyoxalkyl) amines by the action of an alkali metal salt of a monoalkyl ether of an ethylene glycol and a tris (haloethyl) amine.

Aucun des documents ci-dessus cités ne donne un enseignement quant à la préparation sélective d'aminoalcools présentant un atome d'azote trisubstitué par deux chaînes polyoxaalkylés ou arylés et une chaine polyoxahydroxylée présentant un nombre bien défini de motifs oxyalky- lènes.None of the documents cited above teaches as to the selective preparation of amino alcohols having a nitrogen atom trisubstituted by two polyoxaalkylated or arylated chains and a polyoxahydroxylated chain having a well defined number of oxyalkylene units.

Selon l'invention le procédé de préparation d'aminoalcools polyoxaalkylés ou polyoxaarylés de formule:

Figure imgb0003
formule dans laquelle:

  • - R1, R2, R3 et R4 sont semblables ou différents et représentent:
    • · un atome d'hydrogène
    • · un radical alkyle contenant de 1 à 4 atomes de carbone
  • - R5représente:
    • ·un radical alkyle contenant de 1 à 12 atomes de carbone, éventuellement substitué par un groupe phényle
    • ·un radical cycloalkyle contenant de 3 à 12 atomes de carbone
    • ·un radical phényle éventuellement substitué par un groupe alkyle contenant de 1 à 12 atomes de carbone
  • - n est un nombre entier supérieur ou égal à 1 et inférieur ou égal à 9
  • - m est un nombre entier supérieur ou égal à 1 et inférieur ou égal à 10 est caractérisé en ce que l'on fait réagir un polyalkylène glycol de formule:
    Figure imgb0004
    où R1, R2 et n ont la définition donnée ci-dessus avec une bis (polyoxaalkyl)amine ou bis(polyoxaaryl)amine de formule:
    Figure imgb0005
    ou R3, R4, R5 et m ont la définition donnée ci-dessus, selon un rapport molaire polyalkylène glycol de formule (II)/bis(polyoxaalkyl)amine ou bis(polyoxaaryl)amine de formule III d'au moins 1,5 fois le rapport stoechiométriquement requis pour l'obtention d'un aminoalcool polyoxaalkylé ou polyoxaarylé de formule I, en présence d'un catalyseur d'hydrogénation-déshydrogénation, à une température comprise entre 120 et 220°C, de préférence entre 150 et 200°C, et en ce que l'on sépare l'aminoalcool polyoxaalkylé ou polyoxaarylé de formule I.
According to the invention, the process for the preparation of polyoxaalkylated or polyoxaarylated amino alcohols of formula:
Figure imgb0003
 formula in which:
  • - R 1 , R 2 , R 3 and R 4 are similar or different and represent:
    • · A hydrogen atom
    • · An alkyl radical containing from 1 to 4 carbon atoms
  • - R 5 represents:
    • · An alkyl radical containing from 1 to 12 carbon atoms, optionally substituted by a phenyl group
    • · A cycloalkyl radical containing from 3 to 12 carbon atoms
    • · A phenyl radical optionally substituted by an alkyl group containing from 1 to 12 carbon atoms
  • - n is an integer greater than or equal to 1 and less than or equal to 9
  • - m is an integer greater than or equal to 1 and less than or equal to 10 is characterized in that a polyalkylene glycol of formula is reacted:
    Figure imgb0004
     where R 1 , R 2 and n have the definition given above with a bis (polyoxaalkyl) amine or bis (polyoxaaryl) amine of formula:
    Figure imgb0005
     or R 3 , R 4 , R 5 and m have the definition given above, according to a polyalkylene glycol molar ratio of formula (II) / bis (polyoxaalkyl) amine or bis (polyoxaaryl) amine of formula III of at least 1 , 5 times the stoichiometrically required ratio for obtaining a polyoxaalkylated or polyoxaaryl amino alcohol of formula I, in the presence of a hydrogenation-dehydrogenation catalyst, at a temperature between 120 and 220 ° C, preferably between 150 and 200 ° C, and in that the polyoxaalkylated or polyoxaarylated amino alcohol of formula I is separated.

La présente invention vise à titre préférentiel un procédé de préparation d'aminoalcools polyoxaalkylés ou polyoxaarylés de formule (I) dans lesquels:

  • - Ri, R2, R3, R4 sont semblables ou différents et représentent:
    • · un atome d'hydrogène
    • ·un radical méthyle
  • - R5représente:
    • · un radical alkyle contenant de 1 à 6 atomes de carbone,
      et tout particulièrement de 1 à 4 atomes de carbone,
      éventuellement substitué par un groupe phényle;
    • ·un radical cyclohexyle
    • ·un radical phényle éventuellement substitué par un groupe alkyle contenant de 1 à 4 atomes de carbone
  • - n représente un nombre entier supérieur ou égal à 1 et inférieur ou égal à 5, et tout particulièrement égal à 1, 2 ou 3
  • - m représente un nombre entier supérieur ou égal à 1 et inférieur ou égal à 6, et tout particulièrement égal à 1,2,3 ou 4.
The present invention preferably relates to a process for the preparation of polyoxaalkylated or polyoxaarylated amino alcohols of formula (I) in which:
  • - R i , R 2 , R 3 , R 4 are similar or different and represent:
    • · A hydrogen atom
    • · A methyl radical
  • - R 5 represents:
    • · An alkyl radical containing from 1 to 6 carbon atoms,
      and very particularly from 1 to 4 carbon atoms,
      optionally substituted with a phenyl group;
    • · A cyclohexyl radical
    • · A phenyl radical optionally substituted by an alkyl group containing from 1 to 4 carbon atoms
  • - n represents an integer greater than or equal to 1 and less than or equal to 5, and very particularly equal to 1, 2 or 3
  • - m represents an integer greater than or equal to 1 and less than or equal to 6, and very particularly equal to 1,2,3 or 4.

A titre d'exemples d'aminoalcools polyoxaalkylés pouvant être préparés selon le procédé de la présente invention, on peut citer:

  • - le N(hydroxy-5'oxa-3'pentyl)aza-5 dioxa-2,8 nonane
  • - le N(hydroxy-5'oxa-3'pentyl)aza-6 dioxa-3,9 undecane
  • - le N(hydroxy-5'oxa-3'pentyl)aza-7 diox-4,10 tridécane
  • - le N(hydroxy-5'oxa-3'pentyl)aza-8 dioxa-5,11 pentadecane
  • - le N(hydroxy-5'oxa-3'pentyl)aza-8 tetraoxa-2,5,11,14 pentadecane
  • - le N(hydroxy-5'oxa-3'pentyl)aza-9 tetraoxa-3,6,12,15 heptadecane
  • - le N(hydroxy-5'oxa-3'pentyl)aza-10 tetraoxa-4,7,13,16 nonadecane
  • - le N(hydroxy-5'oxa-3'pentyl)aza-11 tetraoxa-5,8,14,17 heneicosane
  • - le N(hydroxy-5'oxa-3'pentyl)aza-11 hexaoxa-2,5,8,14,17,20 heneicosane
  • - le N(hydroxy-5'oxa-3'pentyl)aza-12 hexaoxa-3,6,9,15,18,21 tricosane
  • - le N(hydroxy-5'oxa-3'pentyl)aza-13 hexaoxa-4,7,10,16,19,22 pentacosane
  • - le N(hydroxy-5'oxa-3'pentyl)aza-14 hexaoxa-5,8,11,17,20,23 heptacosane
    ayant pour formule:
    Figure imgb0006
    avecm=1 à 3 et p=1 à 4
  • - le N(hydroxy-8'dioxa-3,6'octyl)aza-5 dioxa-2,8 nonane
  • - le N(hydroxy-8'dioxa-3,6'octyl)aza-6 dioxa-3,9 undecane
  • - le N(hydroxy-8'dioxa-3,6'octyl)aza-7 dioxa-4,10tridecane
  • - le N(hydroxy-8'dioxa-3,6'octyl)aza-8 dioxa-5,11 pentadecane
  • - le N(hydroxy-8'dioxa-3,6'octyl)aza-8 tetraoxa-2,5,11,14 pentadecane
  • - le N(hydroxy-8'dioxa-3,6'octyl)aza-9 tetraoxa-3,6,12,15 heptadecane
  • - le N(hydroxy-8'dioxa-3,6'octyl)aza-10 tetraoxa-4,7,13,16 nonadecane
  • - le N(hydroxy-8'dioxa-3,6'octyl)aza-11 tetraoxa-5,8,14,17 heneicosane
  • - le N(hydroxy-8'dioxa-3,6'octyl)aza-11 hexaoxa-2,5,8,14,17,20 heneicosane
  • - le N(hydroxy-8'dioxa-3,6'octyl)aza-12 hexaoxa-3,6,9,15,18,21 tricosane
  • - le N(hydroxy-8'dioxa-3,6'octyl)aza-13 hexaoxa-4,7,10,16,19,22 pentacosane
  • - le N(hydroxy-8'dioxa-3,6'octyl)aza-14 hexaoxa-5,8,11,17,20,23 heptacosane
    ayant pourformule:
    Figure imgb0007
    avec m=1 à 3 et p = 1 à 4
  • - le N(hydroxy-11'trioxa-3',6',9'undecyl)aza-5 dioxa-2,8 nonane
  • - le N(hydroxy-11'trioxa-3',6',9'undecyl)aza-6 dioxa-3,9 undecane
  • - le N(hydroxy-11'trioxa-3',6',9'undecyl)aza-7 dioxa-4,10tridecane
  • - le N(hydroxy-11'trïoxa-3',6',9'undecyl)aza-8 dioxa-5,11 pentadecane
  • - le N(hydroxy-11'trioxa-3',6',9'undecyl)aza-8 tetraoxa-2,5,11,14 pentadecane
  • - le N(hydroxy-11'trioxa-3',6',9'undecyl)aza-9 tetraoxa-3,6,12,15 heptadecane
  • - le N(hydroxy-11'trioxa-3',6',9'undecyl)aza-10 tetraoxa-4,7,13,16 nonadecane
  • - le N(hydroxy-11'trioxa-3',6',9'undecyl)aza-11 tetraoxa-5,8,14,17 heneicosane
  • - le N(hydroxy-11'trioxa-3',6',9'undecyl)aza-11 hexaoxa-2,5,8,14,17,20 heneicosane
  • - le N(hydroxy-11'trioxa-3',6',9'undecyl)aza-12 hexaoxa-3,6,9,15,18,21 tricosane
  • - le N(hydroxy-11'trioxa-3',6',9'undecyl)aza-13 hexaoxa-4,7,10,16,19,22 pentacosane
  • - le N(hydroxy-11'trioxa-3',6',9'undecyl)aza-14 hexaoxa-5,8,11,17,20,23 heptacosane
    ayant pour formule:
    Figure imgb0008
    avecm=1 à 3 et p = 1 à 4
    ainsi que les aminoalcools polyoxaarylés ayant pour formule:
    Figure imgb0009
    avecn=1 à 3 et m =1 à 3
As examples of polyoxaalkylated amino alcohols which can be prepared according to the process of the present invention, there may be mentioned:
  • - N (hydroxy-5'oxa-3'-pentyl) aza-5-dioxa-2,8 nonane
  • - N (hydroxy-5'-oxa-3'pentyl) aza-6-3,9 dioxa undecane
  • - N (hydroxy-5'oxa-3'pentyl) aza-7 diox-4,10 tridecane
  • - N (hydroxy-5'-oxa-3 'pentyl) aza-dioxa-8 5.11 pentadecane
  • - N (hydroxy-5'oxa-3'pentyl) aza-8 tetraoxa-2,5,11,14 pentadecane
  • - N (hydroxy-5'oxa-3'pentyl) aza-9 tetraoxa-3,6,12,15 heptadecane
  • - N (hydroxy-5'oxa-3'pentyl) aza-10 tetraoxa-4,7,13,16 nonadecane
  • - N (hydroxy-5'-oxa-3 'pentyl) aza-5,8,14,17-tetraoxa 11 heneicosane
  • - N (hydroxy-5'oxa-3'pentyl) aza-11 hexaoxa-2,5,8,14,17,20 heneicosane
  • - N (hydroxy-5'oxa-3'pentyl) aza-12 hexaoxa-3,6,9,15,18,21 tricosan
  • - N (hydroxy-5'oxa-3'pentyl) aza-13 hexaoxa-4,7,10,16,19,22 pentacosane
  • - N (hydroxy-5'oxa-3'pentyl) aza-14 hexaoxa-5,8,11,17,20,23 heptacosane
    having the formula:
    Figure imgb0006
     with m = 1 to 3 and p = 1 to 4
  • - N (hydroxy-8 'dioxa-3,6'octyl) aza-5-dioxa-2,8 nonane
  • - N (hydroxy-8'dioxa-3,6'octyl) aza-6 dioxa-3,9 undecane
  • - N (hydroxy-8'dioxa-3,6 ' octyl) aza-7 dioxa-4,10tridecane
  • - N (hydroxy-8'dioxa-3,6'octyl) aza-8 dioxa-5.11 pentadecane
  • - N (hydroxy-8'dioxa-3,6 ' octyl) aza-8 tetraoxa-2,5,11,14 pentadecane
  • - N (hydroxy-8'dioxa-3,6'octyl) aza-9 tetraoxa-3,6,12,15 heptadecane
  • - N (hydroxy-8 'dioxa-3,6'octyl) aza-4,7,13,16-tetraoxa 10 nonadecane
  • - N (hydroxy-8'dioxa-3,6'octyl) aza-11 tetraoxa-5,8,14,17 heneicosane
  • - N (hydroxy-8'dioxa-3,6'octyl) aza-11 hexaoxa-2,5,8,14,17,20 heneicosane
  • - N (hydroxy-8 'dioxa-3,6'octyl) aza-12 hexaoxa-tricosane 3,6,9,15,18,21
  • - N (hydroxy-8'dioxa-3,6'octyl) aza-13 hexaoxa-4,7,10,16,19,22 pentacosane
  • - N (hydroxy-8'dioxa-3,6'octyl) aza-14 hexaoxa-5,8,11,17,20,23 heptacosane
    having the formula:
    Figure imgb0007
     with m = 1 to 3 and p = 1 to 4
  • - N (hydroxy-11'trioxa-3 ', 6', 9'undecyl) aza-5 dioxa-2,8 nonane
  • - N (hydroxy-11'trioxa-3 ', 6', 9'undecyl) aza-6 dioxa-3,9 undecane
  • - N (hydroxy-11'trioxa-3 ', 6', 9'undecyl) aza-7 dioxa-4,10tridecane
  • - N (hydroxy-11 ' trioxa-3', 6 ', 9'undecyl) aza-8 dioxa-5.11 pentadecane
  • - N (hydroxy-11'trioxa-3 ', 6', 9'undecyl) aza-8 tetraoxa-2,5,11,14 pentadecane
  • - N (hydroxy-11'trioxa-3 ', 6', 9'undecyl) aza-9 tetraoxa-3,6,12,15 heptadecane
  • - N (hydroxy-11'trioxa-3 ', 6', 9'undecyl) aza-10 tetraoxa-4,7,13,16 nonadecane
  • - N (hydroxy-11'trioxa-3 ', 6', 9'undecyl) aza-11 tetraoxa-5,8,14,17 heneicosane
  • - N (hydroxy-11'trioxa-3 ', 6', 9'undecyl) aza-11 hexaoxa-2,5,8,14,17,20 heneicosane
  • - N (hydroxy-11'trioxa-3 ', 6', 9'undecyl) aza-12 hexaoxa-3,6,9,15,18,21 tricosane
  • - N (hydroxy-11'trioxa-3 ', 6', 9'undecyl) aza-13 hexaoxa-4,7,10,16,19,22 pentacosane
  • - N (hydroxy-11'trioxa-3 ', 6', 9'undecyl) aza-14 hexaoxa-5,8,11,17,20,23 heptacosane
    having the formula:
    Figure imgb0008
     with m = 1 to 3 and p = 1 to 4
    as well as polyoxaarylated amino alcohols having the formula:
    Figure imgb0009
     withn = 1 to 3 and m = 1 to 3

Pour une bonne réalisation du procédé faisant l'objet de la présente invention, on pourra choisir des catalyseurs au nickel, du type nickel Raney ou Harshaw; la quantité de catalyseur pourra être comprise entre 1 et 15% du poids de bis(po- lyoxaalkyl)amine ou bis(polyoxaaryl)amine et de préférence entre 2 et 6%.For a good implementation of the process which is the subject of the present invention, it is possible to choose nickel catalysts, of the Raney or Harshaw nickel type; the amount of catalyst may be between 1 and 15% of the weight of bis (polyoxaalkyl) amine or bis (polyoxaaryl) amine and preferably between 2 and 6%.

Le rapport molaire polyalkylène glycol de formule (II)/bis (polyoxaalkyl)amine ou bis(polyoxaaryl)amine de formule (III) pourra également être compris entre 1, 5 et 10 fois la stoechiométrie et de préférence entre 2 et 6 fois la stoechiométrie.The polyalkylene glycol molar ratio of formula (II) / bis (polyoxaalkyl) amine or bis (polyoxaaryl) amine of formula (III) may also be between 1, 5 and 10 times the stoichiometry and preferably between 2 and 6 times the stoichiometry .

Le procédé faisant l'objet de l'invention pourra de préférence être réalisé en présence d'hydrogène, à une pression inférieure à 20 bars, et généralement à pression autogène, sous agitation violente jusqu'à disparition du polyalkylène glycol; cette opération dure de 2 à 10 heures et généralement de 3 à 4 heures. La quantité d'hydrogène pouvant être utilisée est de l'ordre de 1 à 10% du poids d'alkylène glycol mis en oeuvre et de préférence de l'ordre de 1 à 5%.The process which is the subject of the invention may preferably be carried out in the presence of hydrogen, at a pressure below 20 bars, and generally at autogenous pressure, with vigorous stirring until the polyalkylene glycol disappears; this operation lasts from 2 to 10 hours and general 3 to 4 hours. The amount of hydrogen that can be used is of the order of 1 to 10% of the weight of alkylene glycol used and preferably of the order of 1 to 5%.

L'eau formée au cours de la réaction pourra être éliminée du milieu réactionnel à l'aide d'un courant gazeux, tel que l'hydrogène quand celui- ci a été mis en œuvre ou de l'azote.The water formed during the reaction can be removed from the reaction medium using a gas stream, such as hydrogen when the latter has been used or nitrogen.

A titre d'exemples de polyalkylène glycol pouvant être mis en œuvre, on peut citer:

  • - le diéthylène glycol
  • - le triéthylène glycol
  • - le tétraéthylène glycol.
As examples of polyalkylene glycol which can be used, there may be mentioned:
  • - diethylene glycol
  • - triethylene glycol
  • - tetraethylene glycol.

A titre d'exemples de bis(polyoxaalkyl)amines ou bis(polyoxaaryl)amines pouvant être mis en œuvre, on peut citer:

  • - l'aza-5 dioxa-2,8 nonane
  • - l'aza-6 dioxa-3,9 undecane
  • - l'aza-7dioxa-4,10tridecane
  • - l'aza-8 dioxa-5,11 pentadecane
  • - 'aza-8 tetraoxa-2,5,11,14 pentadecane
  • - l'aza-9 tetraoxa-3,6,12,15 heptadecane
  • - l'aza-10 tetraoxa-4,7,13,16 nonadecane
  • - l'aza-1 tetraoxa-5,8,14,17 heneicosane
  • - l'aza-1 hexaoxa-2,5,8,14,17,20 heneicosane
  • - l'aza-12 hexaoxa-3,6,9,15,18,21 tricosane
  • - l'aza-13 hexaoxa-4,7,10,16,19,22 pentacosane
  • - l'aza-14 hexaoxa-5,8,11,17,20,23 heptacosane

ayant pourformule:
Figure imgb0010
avecm=1 à 3 et p =1 à 4,
ainsi que celles ayant pour formule:
Figure imgb0011
avec m = 1 à 3.As examples of bis (polyoxaalkyl) amines or bis (polyoxaaryl) amines which can be used, there may be mentioned:
  • - aza-5 dioxa-2,8 nonane
  • - aza-6 dioxa-3,9 undecane
  • - aza-7dioxa-4,10tridecane
  • - aza-8 dioxa-5.11 pentadecane
  • - 'aza-8 tetraoxa-2,5,11,14 pentadecane
  • - aza-9 tetraoxa-3,6,12,15 heptadecane
  • - aza-10 tetraoxa-4,7,13,16 nonadecane
  • - aza-1 tetraoxa-5,8,14,17 heneicosane
  • - aza-1 hexaoxa-2,5,8,14,17,20 heneicosane
  • - aza-12 hexaoxa-3,6,9,15,18,21 tricosan
  • - aza-13 hexaoxa-4,7,10,16,19,22 pentacosane
  • - aza-14 hexaoxa-5,8,11,17,20,23 heptacosane

having the formula:
Figure imgb0010
 with m = 1 to 3 and p = 1 to 4,
as well as those having the formula:
Figure imgb0011
 with m = 1 to 3.

Les aminoalcools polyoxaalkylés ou polyoxaarylés obtenus selon le procédé de l'invention peuvent être utilisés comme agents de complexation de cations. La présente invention a également pour objet cette application.The polyoxaalkylated or polyoxaarylated amino alcohols obtained according to the process of the invention can be used as cation complexing agents. The present invention also relates to this application.

Parmi les cations pouvant être complexés par lesdits aminoalcools polyoxaalkylés ou polyoxaarylés on peut citer: NH4 + et les cations dérivés des métaux des groupes IA à VIIA, VIII, IB à VB (Société Chimique de France) en particulier ceux dérivés des métaux alcalins ou alcalino-terreux tels que: Na, K, Li, Cs, Ca, Ba.Among the cations which may be complexed by said polyoxaalkylated or polyoxaarylated amino alcohols, mention may be made of: NH 4 + and the cations derived from the metals of groups IA to VII A , VIII, I B to V B (Société Chimique de France) in particular those derived from alkali or alkaline earth metals such as: Na, K, Li, Cs, Ca, Ba.

La complexation par les aminoalcools polyoxaalkylés ou polyoxaarylés de l'invention, de sels minéraux ou organiques des métaux ci-dessus cités ou de sels d'ammonium, permet de solubiliser lesdits sels ou d'améliorer la solubilité desdits sels dans des solvants organiques dans lesquels ils sont habituellement insolubles ou peu solubles.Complexation by the polyoxaalkylated or polyoxaarylated amino alcohols of the invention, of inorganic or organic salts of the metals mentioned above or of ammonium salts, makes it possible to dissolve said salts or to improve the solubility of said salts in organic solvents in which they are usually insoluble or poorly soluble.

Les exemples suivants sont donnés à titre indicatif et ne peuvent être considérés comme une limite du domaine et de l'esprit de l'invention.The following examples are given for information only and cannot be considered as limiting the scope and spirit of the invention.

Exemple 1Example 1

Préparation du N(hydroxy 5' oxa 3' pentyl)aza 9 tétraoxa 3,6,12,15 heptadécane:

Figure imgb0012
Preparation of N (hydroxy 5 'oxa 3' pentyl) aza 9 tetraoxa 3,6,12,15 heptadecane:
Figure imgb0012

Dans un ballon tétracol de 2 litres, équipé d'une agitation, d'une arrivée d'hydrogène, d'une colonne et d'un condenseur pour recueillir l'eau, on charge:

Figure imgb0013
In a 2 liter tetracol flask, equipped with a stirrer, a hydrogen inlet, a column and a condenser to collect the water, we charge:
Figure imgb0013

On agite sous un courant d'hydrogène (11/mn) et on chauffe 3 heures à 170°C. On recueille 106 g d'eau et de produits légers correspondant à la déshydratation du diéthylène glycol. Après refroidissement, et séparation du Nickel Raney, le mélange est soumis à distillation pour récupérer 888g de diéthylène glycol et 280 du produit cherché qui bout à Eb1:193°.Stirred under a stream of hydrogen (11 / min) and heated for 3 hours at 170 ° C. 106 g of water and light products are collected, corresponding to the dehydration of diethylene glycol. After cooling, and separation of the Nickel Raney, the mixture is subjected to distillation to recover 888 g of diethylene glycol and 280 of the sought product which boils at Eb 1 : 193 °.

Le rendement atteint 55% sur l'amine secondaire engagée.The yield reaches 55% on the secondary amine used.

Exemple 2Example 2

Préparation du N(hydroxy-8' dioxa 3',6' octyl)aza 9 tétraoxa 3,6,12,15 heptadécane:

Figure imgb0014
Preparation of N (8-hydroxy 3 'dioxa, 6' octyl) aza 9 tetraoxa 3,6,12,15 heptadecane:
Figure imgb0014

Dans le même appareillage que l'exemple 1, et dans les mêmes conditions de travail, on fait réagir:

Figure imgb0015
In the same apparatus as in Example 1, and under the same working conditions, the following are reacted:
Figure imgb0015

Après 3 heures de chauffage à 180°C, puis filtration du Nickel Raney, le mélange est soumis à distillation pour éliminer le triéthylène glycol. On récupère 610 du produit attendu sous forme d'un liquide brun foncé présentant une pureté de 88,1%.After 3 hours of heating to 180 ° C., then filtration of the Nickel Raney, the mixture is subjected to distillation to remove the triethylene glycol. 610 of the expected product are recovered in the form of a dark brown liquid having a purity of 88.1%.

Le rendement sur l'amine secondaire chargée atteint 71 %.The yield on the charged secondary amine reaches 71%.

Exemple 3Example 3

Préparation du N(hydroxy 8' dioxa 3',6' octyl) aza 11 hexaoxa 2,5,8,14,17,20 heneicosane.

Figure imgb0016
Preparation of N (hydroxy 8 'dioxa 3', 6 'octyl) aza 11 hexaoxa 2,5,8,14,17,20 heneicosane.
Figure imgb0016

Dans les mêmes conditions qu'à l'exemple 1, on fait réagir:

  • - aza 11 hexaoxa 2,5,8,14,17,20 heneicosane
    250 g (0,80 mole)
  • - triéthylène glycol 550 g (3,66 moles)
  • - NickeyRaney déshydraté 50 g
Under the same conditions as in Example 1, the reaction is carried out:
  • - aza 11 hexaoxa 2,5,8,14,17,20 heneicosane
    250 g (0.80 mole)
  • - triethylene glycol 550 g (3.66 moles)
  • - NickeyRaney dehydrated 50 g

Après 5 heures de réaction à 180° sous courant d'hydrogène, le Nickel Raney est filtré et le filtrat est étété jusqu'à 300° sous 0,1 mmHg (13,3 Pa). On obtient 325 g de l'aminoalcool cherché, soit un rendement de 92,2%.After 5 hours of reaction at 180 ° under a stream of hydrogen, the Nickel Raney is filtered and the filtrate is summer up to 300 ° under 0.1 mmHg (13.3 Pa). 325 g of the desired amino alcohol are obtained, ie a yield of 92.2%.

Exemple 4Example 4

Préparation du N(hydroxy-5' oxa-3' pentyl)aza-8 tetraoxa-3,6,11,14 pentadécane.

Figure imgb0017
Preparation of N (5-hydroxy-oxa-3 'pentyl) aza-8 tetraoxa-3,6,11,14 pentadecane.
Figure imgb0017

Dans les mêmes conditions qu'à l'exemple 1, on fait réagir:

  • - aza-8tétraoxa-3,6,11,14pentadécane
    676,5 g (3 moles)
  • - diéthylèneglycol 1285 g (12 moles)
  • - nickel Raney déshydraté 218 g
Under the same conditions as in Example 1, the reaction is carried out:
  • - aza-8tetraoxa-3,6,11,14pentadecane
    676.5 g (3 moles)
  • - diethylene glycol 1285 g (12 moles)
  • - dehydrated Raney nickel 218 g

On maintient 3 heures à 180-185°C sous un courant de 2g/h d'hydrogène.Maintained for 3 hours at 180-185 ° C under a stream of 2 g / h of hydrogen.

Après séparation du nickel Raney, la masse est distillée pour récupérer l'excès de diéthylèneglycol et 662 de l'aminoalcool attendu qui bout à Eb1 = 200°C.After separation of the Raney nickel, the mass is distilled to recover the excess of diethylene glycol and 662 of the expected amino alcohol which boils at Eb 1 = 200 ° C.

Le rendement par rapport à l'amine secondaire engagée est de 71,5%.The yield relative to the secondary amine used is 71.5%.

Exemple 5Example 5

Préparation du N(hydroxy-8' dioxa-3',6' oc- tvl)aza-8 tétraoxa-2.5.11.14 pentadécane.

Figure imgb0018
Preparation of N (8-hydroxy-dioxa-3 ', 6' oc-tvl) aza-8 tetraoxa-2.5.11.14 pentadecane.
Figure imgb0018

Dans les mêmes conditions qu'à l'exemple 1, on fait réagir:

Figure imgb0019
Under the same conditions as in Example 1, the reaction is carried out:
Figure imgb0019

Après 3 heures de chauffage à 180°C, filtration du nickel Raney et distillation pour éliminer le triéthylène glycol, on récupère 508 de l'aminoalcool attendu qui bout à Eb0,3 = 193°C.After 3 hours of heating to 180 ° C., filtration of the Raney nickel and distillation to remove the triethylene glycol, 508 of the expected amino alcohol are recovered which boils at Eb 0.3 = 193 ° C.

Le rendement par rapport à l'amine secondaire est de 72%.The yield relative to the secondary amine is 72%.

Exemple 6Example 6

Propriété complexante du N(hydroxy 8' dioxa 3',6' octyl)aza II hexaoxa 2,5,8,14,17,20 heneicosane.Complexing property of N (hydroxy 8 'dioxa 3', 6 'octyl) aza II hexaoxa 2,5,8,14,17,20 heneicosane.

Solùbilisation des thiocyanates alcalins dans le chlorure de méthylène.Solubilization of alkali thiocyanates in methylene chloride.

Ce test mettant en évidence la propriété complexante du produit préparé à l'exemple 3 est réalisé comme suit:

  • Dans un erlenmeyer de 50 ml équipé d'un réfrigérant ascendant et d'un agitateur magnétique, on introduit 10 ml de chlorure de méthylène anhydre et purifié (c'est-à-dire exempt de stabilisant).
This test highlighting the complexing property of the product prepared in Example 3 is carried out as follows:
  • 10 ml of anhydrous and purified methylene chloride (that is to say free from stabilizer) are introduced into a 50 ml Erlenmeyer flask equipped with an ascending cooler and a magnetic stirrer.

On ajoute ensuite:

  • - 0,001 mole d'un thiocyanate alcalin choisi parmi les thiocyanates de Li, Na et K;
  • - 0,001 mole d'agent complexant à tester.
Then we add:
  • - 0.001 mole of an alkali thiocyanate chosen from thiocyanates of Li, Na and K;
  • - 0.001 mole of complexing agent to be tested.

Après avoir agité le mélange pendant 10 mm à la température ambiante, on centrifuge; la solution claire ainsi obtenue est analysée par spectrométrie de flamme.After the mixture has been stirred for 10 mm at room temperature, it is centrifuged; the clear solution thus obtained is analyzed by flame spectrometry.

Le test est également réalisé en l'absence d'agent complexant à tester.The test is also carried out in the absence of complexing agent to be tested.

Les résultats obtenus sont les suivants:

  • - Solubilisation de Li S C N
  • - solubilité mesurée: 690 mg/I
  • - solubilité maximum calculée: 690 mg/I
  • - taux de solubilisation: 100%
  • - complexes formé:
    Figure imgb0020
  • - Solubilité mesurée sans agent complexant: <1 mg/1
  • - Solubilisation de NaSCN
  • - Solubilité mesurée: 2300 mg/l
  • - solubilité maximum calculée: 2300 mg/l
  • - taux de solubilisation: 100%
  • - complexe formé:
    Figure imgb0021
  • - Solubilité mesurée sans agent complexant: <1 mg/I
  • - Solubilisation de KSCN
  • - solubilité mesurée: 3380 mg/I
  • - solubilité maximum calculée: 3910 mg/l
  • - taux de solubilisation: 86,4%
  • - complexe formé:
    Figure imgb0022
The results obtained are as follows:
  • - Solubilization of Li SCN
  • - measured solubility: 690 mg / I
  • - maximum calculated solubility: 690 mg / I
  • - solubilization rate: 100%
  • - complexes formed:
    Figure imgb0020
  • - Solubility measured without complexing agent: <1 mg / 1
  • - Solubilization of NaSCN
  • - Measured solubility: 2300 mg / l
  • - maximum calculated solubility: 2300 mg / l
  • - solubilization rate: 100%
  • - complex formed:
    Figure imgb0021
  • - Solubility measured without complexing agent: <1 mg / I
  • - Solubilization of KSCN
  • - measured solubility: 3380 mg / I
  • - maximum calculated solubility: 3910 mg / l
  • - solubilization rate: 86.4%
  • - complex formed:
    Figure imgb0022

Les résultats ci-dessus peuvent être résumés dans le tableau suivant:

Figure imgb0023
The above results can be summarized in the following table:
Figure imgb0023

Exemple 7Example 7

Propriété complexante du N(hydroxy-5' oxa-3' pentyl) aza-8 tétraoxa-3,6,11,14 pentadécane Solubilisation des thiocyantes alcalins dans le chlorure de méthylène.Complexing property of N (5-hydroxy-oxa-3 'pentyl) aza-8 tetraoxa-3,6,11,14 pentadecane Solubilization of alkaline thiocyants in methylene chloride.

Le test décrit à l'exemple 6 est réalisé en mettant en oeuvre comme agent complexant à tester le produit de l'exemple 4.The test described in Example 6 is carried out using as a complexing agent to test the product of Example 4.

Les résultats sont les suivants:

Figure imgb0024

  • - taux de solubilisation de LiSCN: 97% NaSCN: 98% KSCN: 93%
  • - complexes formés:
    Figure imgb0025
The results are as follows:
Figure imgb0024
  • - LiSCN solubilization rate: 97% NaSCN: 98% KSCN: 93%
  • - complexes formed:
    Figure imgb0025

Exemple 8Example 8

Propriété complexante du N(hydroxy-8' dioxa-3',6' octyl/aza-8 tétraoxa-2,5,11,14 pentadécaneComplexing property of N (8-hydroxy-dioxa-3 ', 6' octyl / aza-8 tetraoxa-2,5,11,14 pentadecane

Solubilisation des thiocyanates alcalins dans le chlorure de méthylène.Solubilization of alkali thiocyanates in methylene chloride.

Le test décrit à l'exemple 6 est réalisé en mettant en œuvre comme agent complexant à tester le produit de l'exemple 5. Les résultats sont les suivants:

Figure imgb0026

  • - taux de solubilisation de LiSCN: 99% NaSCN: 100% KSCN: 93%
  • - complexes formés:
    Figure imgb0027
The test described in Example 6 is carried out using as a complexing agent to test the product of Example 5. The results are as follows:
Figure imgb0026
  • - solubilization rate of LiSCN: 99% NaSCN: 100% KSCN: 93%
  • - complexes formed:
    Figure imgb0027

Claims (14)

1. Process for the preparation of polyoxaalkylated or polyoxaarylated aminoalcohols of the formula:
Figure imgb0042
in which formula:
- Ri, R2, R3 and R4 are similar or different and represent:
· a hydrogen atom or
· an alkyl radical containing from 1 to 4 carbon atoms,
- Rs represents:
· an alkyl radical containing from 1 to 12 carbon atoms, which is optionally substituted by a phenyl group,
· a cycloalkyl radical containing from 3 to 12 carbon atoms, or
· a phenyl radical optionally substituted by an alkyl group containing from 1 to 12 carbon atoms,
- n is an integrer greater than or equal to 1 and less than or equal to 9, and
- m is an integrer greater than or equal to 1 and less than or equal to 10, the said process being characterised in that a polyalkylene glycol of the formula:
Figure imgb0043
is reacted with a bis-(polyoxaalkyl)-amine or bis-(polyoxaaryl)-amine of the formula:
Figure imgb0044
in a molar ratio of polyalkylene glycol of the formula II/bis-(polyoxaalkyl)-amine or bis-(polyoxaaryl)-amine of the formula III which is at least 1.5 times the ratio stoichiometrically required to obtain a polyoxaalkylated or polyoxaarylated aminoalcohol of the formula I, in the presence of a hydrogenation/dehydrogenation catalyst, at a temperature of between 120 and 220°C, and in that the polyoxaalkylated or polyoxaarylated aminoalcohol of the formula I is separated off.
2. Process according to Claim 1, characterised in that:
- Ri, R2, R3 and R4 are similar or different and represent:
· a hydrogen atom or
· a methyl radical,
- R5 represents:
. an alkyl radical containing from 1 to 6 carbon atoms, which is optionally substituted by a phenyl group,
· a cyclohexyl radical or
· a phenyl radical optionally substituted by an alkyl group containing from 1 to 4 carbon atoms,
- n represents an integrer greater than or equal to 1 and less than or equal to 5, and
- m represents an integer greater than or equal to 1 and less than or equal to 6.
3. Process according to Claim 1 or Claim 2, characterised in that if R5 represents an alkyl radical, it contains from 1 to 4 carbon atoms.
4. Process according to Claim 1 or Claim 2, characterised in that n is equal to 1, 2 or 3 and m is equal to 1, 2, 3 or 4.
5. Process according to any one of Claims 1 to 4, characterised in that the reaction of the polyalkyleneglycol with the bis-(polyoxaalkyl)-amine or bis-(polyoxaaryl)-amine is carried out at a temperature of between 150 and 200°C.
6. Process according to any one of Claims 1 to 4, characterised in that the catalyst is chosen from amongst Raney and Harshaw nickel catalysts and is used in an amount of between 1 and 15% of the weight of bis(polyoxaalkyl)-amine or bis-(polyoxaaryl)-amine
7. Process according to Claim 6, characterised in that the amount of catalyst is between 2 and 6% of the weight of bis-(polyoxaalkyl)-amine or bis-(polyoxaaryl)-amine
8. Process according to any one of Claims 1 to 4, characterised in that the molar ratio of polyalkylene glycol/bis-(polyoxaalkyl)-amine or bis-(polyoxaaryl)-amine is between 1.5 and 10 times the stoichiometric ratio.
9. Process according to Claim 8, characterised in that the said molar ratio is between 2 and 6 times the stoichiometric ratio.
10. Process according to any one of Claims 1 to 4, characterised in that the reaction of the polyalkylene glycol with the bis-(polyoxaalkyl)-amine or bis-(polyoxaaryl)-amine is carried out in the presence of hydrogen in an amount corresponding to 1-10% of the weight of alkylene glycol.
11. Process according to Claim 10, characters ed in that the amount of hydrogen corresponds to 1 to 5% of the weight of alkylene glycol.
12. Process according to Claim 1, characterised in that di-, tri- or tetra-ethylene glycol is reacted with a bis-(polyoxaalkyl)-amine of the formula:
Figure imgb0045
in which m is equal to 1, 2 or 3 and p is equal to 1, 2, or 4, and in that the polyoxyalkylated aminoalcohol of the formula:
Figure imgb0046
in which n is respectively equal to 1, 2 or 3, is separated off.
13. Process according to Claim 1, characterised in that di-, tri- ortetra-ethylene glycol is reacted with a bis-(polyoxaaryl)-amine of the formula:
Figure imgb0047
in which m is equal to 1, 2 or 3, and in that the po- lyoxyarylated aminoalcohol of the formula:
Figure imgb0048
in which n is respectively equal to 1, 2 or 3, is separated off
14. Application of the polyoxaalkylated or polyoxaarylated aminoalcohols obtained according to any one of the preceding claims, as complexing agents for cations.
EP81401325A 1980-08-27 1981-08-20 Process for preparation of aminoalcohols polyoxa-alkylated or polyoxa-arylated and their use as cation complexing agents Expired EP0047206B1 (en)

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